Assessment of the consistency of H2O line intensities over the near-infrared using sun-pointing ground-based Fourier transform spectroscopy

We report on the consistency of water vapour line intensities in selected spectral regions between 800–12,000 cm−1 under atmospheric conditions using sun-pointing Fourier transform infrared spectroscopy. Measurements were made across a number of days at both a low and high altitude field site, sampling a relatively moist and relatively dry atmosphere. Our data suggests that across most of the 800–12,000 cm−1 spectral region water vapour line intensities in recent spectral line databases are generally consistent with what was observed. However, we find that HITRAN-2008 water vapour line intensities are systematically lower by up to 20% in the 8000–9200 cm−1 spectral interval relative to other spectral regions. This discrepancy is essentially removed when two new linelists (UCL08, a compilation of linelists and ab-initio calculations, and one based on recent laboratory measurements by Oudot et al. (2010) [10] in the 8000–9200 cm−1 spectral region) are used. This strongly suggests that the H2O line strengths in the HITRAN-2008 database are indeed underestimated in this spectral region and in need of revision. The calculated global-mean clear-sky absorption of solar radiation is increased by about 0.3 W m−2 when using either the UCL08 or Oudot line parameters in the 8000–9200 cm−1 region, instead of HITRAN-2008. We also found that the effect of isotopic fractionation of HDO is evident in the 2500–2900 cm−1 region in the observations.

Identification of metabolites in human hepatic bile using 800 MHz 1H NMR spectroscopy, HPLC-NMR/MS and UPLC-MS

The first application of high field NMR spectroscopy (800 MHz for 1H observation) to human hepatic bile (as opposed to gall bladder bile) is reported. The bile sample used for detailed investigation was from a donor liver with mild fat infiltration, collected during organ retrieval prior to transplantation. In addition, to focus on the detection of bile acids in particular, a bile extract was analysed by 800 MHz 1H NMR spectroscopy, HPLC-NMR/MS and UPLC-MS. In the whole bile sample, 40 compounds have been assigned with the aid of two-dimensional 1H–1H TOCSY and 1H–13C HSQC spectra. These include phosphatidylcholine, 14 amino acids, 10 organic acids, 4 carbohydrates and polyols (glucose, glucuronate, glycerol and myo-inositol), choline, phosphocholine, betaine, trimethylamine-N-oxide and other small molecules. An initial NMR-based assessment of the concentration range of some key metabolites has been made. Some observed chemical shifts differ from expected database values, probably due to a difference in bulk diamagnetic susceptibility. The NMR spectra of the whole extract gave identification of the major bile acids (cholic, deoxycholic and chenodeoxycholic), but the glycine and taurine conjugates of a given bile acid could not be distinguished. However, this was achieved by HPLC-NMR/MS, which enabled the separation and identification of ten conjugated bile acids with relative abundances varying from approximately 0.1% (taurolithocholic acid) to 34.0% (glycocholic acid), of which, only the five most abundant acids could be detected by NMR, including the isomers glycodeoxycholic acid and glycochenodeoxycholic acid, which are difficult to distinguish by conventional LC-MS analysis. In a separate experiment, the use of UPLC-MS allowed the detection and identification of 13 bile acids. This work has shown the complementary potential of NMR spectroscopy, MS and hyphenated NMR/MS for elucidating the complex metabolic profile of human hepatic bile. This will be useful baseline information in ongoing studies of liver excretory function and organ transplantation.

Early detection of ovarian cancer in samples pre-diagnosis using CA125 and MALDI-MS peaks

Aim: A nested case-control discovery study was undertaken 10 test whether information within the serum peptidome can improve on the utility of CA125 for early ovarian cancer detection. Materials and Methods: High-throughput matrix-assisted laser desorption ionisation mass spectrometry (MALDI-MS) was used to profile 295 serum samples from women pre-dating their ovarian cancer diagnosis and from 585 matched control samples. Classification rules incorporating CA125 and MS peak intensities were tested for discriminating ability. Results: Two peaks were found which in combination with CA125 discriminated cases from controls up to 15 and 11 months before diagnosis, respectively, and earlier than using CA125 alone. One peak was identified as connective tissue-activating peptide III (CTAPIII), whilst the other was putatively identified as platelet factor 4 (PF4). ELISA data supported the down-regulation of PF4 in early cancer cases. Conclusion: Serum peptide information with CA125 improves lead time for early detection of ovarian cancer. The candidate markers are platelet-derived chemokines, suggesting a link between platelet function and tumour development.

Quantitative analysis of mannitol polymorphs: FT-Raman spectroscopy

Mannitol is a polymorphic excipient which is usually used in pharmaceutical products as the beta form, although other polymorphs (alpha and delta) are common contaminants. Binary mixtures containing beta and delta mannitol were prepared to quantify the concentration of the beta form using FT-Raman spectroscopy. Spectral regions characteristic of each form were selected and peak intensity ratios of beta peaks to delta peaks were calculated. Using these ratios, a correlation curve was established which was then validated by analysing further samples of known composition. The results indicate that levels down to 2% beta could be quantified using this novel, non-destructive approach. Potential errors associated with quantitative studies using FT-Raman spectroscopy were also researched. The principal source of variability arose from inhomogeneities on mixing of the samples; a significant reduction of these errors was observed by reducing and controlling the particle size range. The results show that FT-Raman spectroscopy can be used to rapidly and accurately quantitate polymorphic mixtures.

Determination of orientations of aromatic groups in self-assembled peptide fibrils by polarised Raman spectroscopy

In this paper we describe a novel combination of Raman spectroscopy, isotope editing and X-ray scattering as a powerful approach to give detailed structural information on aromatic side chains in peptide fibrils. The orientation of the tyrosine residues in fibrils of the peptide YTIAALLSPYS with respect to the fibril axis has been determined from a combination of polarised Raman spectroscopy and X-ray diffraction measurements. The Raman intensity of selected tyrosine bands collected at different polarisation geometries is related to the values and orientation of the Raman tensor for those specific vibrations. Using published Raman tensor values we solved the relevant expressions for both of the two tyrosine residues present in this peptide. Ring deuteration in one of the two tyrosine side chains allowed for the calculation to be performed individually for both, by virtue of the isotopic shift that eliminates band overlapping. Sample disorder was taken into account by obtaining the distribution of orientations of the samples from X-ray diffraction experiments. The results provide previously unavailable details about the molecular conformation of this peptide, and demonstrate the value of this approach for the study of amyloid fibrils.

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl–DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

Near-infrared integral field spectroscopy of the Homunculus nebula around eta Carinae using Gemini/CIRPASS

This work presents the first integral field spectroscopy of the Homunculus nebula around eta Carinae in the near-infrared spectral region (J band). We confirmed the presence of a hole on the polar region of each lobe, as indicated by previous near-IR long-slit spectra and mid-IR images. The holes can be described as a cylinder of height (i.e. the thickness of the lobe) and diameter of 6.5 and 6.0 x 10(16) cm, respectively. We also mapped the blue-shifted component of He I lambda 10830 seen towards the NW lobe. Contrary to previous works, we suggested that this blue-shifted component is not related to the Paddle but it is indeed in the equatorial disc. We confirmed the claim of N. Smith and showed that the spatial extent of the Little Homunculus matches remarkably well the radio continuum emission at 3 cm, indicating that the Little Homunculus can be regarded as a small H II region. Therefore, we used the optically thin 1.3 mm radio flux to derive a lower limit for the number of Lyman-continuum photons of the central source in eta Car. In the context of a binary system, and assuming that the ionizing flux comes entirely from the hot companion star, the lower limit for its spectral type and luminosity class ranges from O5.5 III to O7 I. Moreover, we showed that the radio peak at 1.7 arcsec NW from the central star is in the same line-of-sight of the `Sr-filament` but they are obviously spatially separated, while the blue-shifted component of He I lambda 10830 may be related to the radio peak and can be explained by the ultraviolet radiation from the companion star.

Nuclear and extended spectra of NGC 1068-I. Hints from near-infrared spectroscopy

We report the first simultaneous zJHK spectroscopy on the archetypical Seyfert 2 galaxy NGC 1068 covering the wavelength region 0.9-2.4 mu m. The slit, aligned in the north-south direction and centred in the optical nucleus, maps a region 300 pc in radius at subarcsec resolution, with a spectral resolving power of 360 km s-1. This configuration allows us to study the physical properties of the nuclear gas including that of the north side of the ionization cone, map the strong excess of continuum emission in the K band and attributed to dust and study the variations, both in flux and profile, in the emission lines. Our results show the following. (1) Mid- to low-ionization emission lines are split into two components, whose relative strengths vary with the position along the slit and seem to be correlated with the jet. (2) The coronal lines are single-peaked and are detected only in the central few hundred of pc from the nucleus. (3) The absorption lines indicate the presence of intermediate age stellar population, which might be a significant contributor to the continuum in the near-IR spectra. (4) Through some simple photoionization models we find photoionization as the main mechanism powering the emitting gas. (5) Calculations using stellar features point to a mass concentration inside the 100-200 pc of about 1010 M(circle dot).

Femtosecond laser ablation on dental hard tissues-Analysis of ablated profile near an interface using local effective intensity

This study evaluated the process of ablation produced by a Ti:Sapphire femtosecond laser under different average powers taking place at the enamel/dentin interface. Based on the geometry of ablated microcavities the effective intensity for ablation was obtained. This study shows the validity for the local effective intensity analysis and allows a quantification of the variation in the ablation geometry taking place at the interface of two naturally different materials. It shows that the variation of the diameter of the ablated region as a function of the cavity depth comes essentially from a mechanism of effective intensity attenuation, as a result of a series of complex effects. Additionally, our data are sufficient to predict that a discontinuity on the ablation profile will occur on the interface between two biological media: enamel-dentin, showing a suddenly jump on the ablated cavity dimensions.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

A comparative study of two different conductive carbon-black pigments, Vulcan XC-72 R and Printex L6, for the electrogeneration of hydrogen peroxide (H(2)O(2)) by reducing dissolved oxygen in an alkaline solution was performed. The materials were physically characterized by X-ray diffraction (XRD), Fourier transform infrared attenuated total reflection (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). XRD shows the presence of SO(2) and ATR-FTIR technique indicates a difference in NO and SO(2) functional groups between the two carbon pigments. XPS indicated presence of SO and NO and more oxygenated acid species on Printex L6. A rotating ring-disk electrode was used for electrochemical analysis of the oxygen reduction reaction (ORR). The results showed that the Printex L6 was better than Vulcan XC-72 R for H(2)O(2) production. Results also indicate that the number of electrons transferred in the ORR for Printex L6 and Vulcan XC-72 R were 2.2 and 2.9, respectively, while the percentages of H(2)O(2) formed were 88% and 51%. Scanning electrochemistry microscopy images confirmed the higher amount of H(2)O(2) formed in the Printex L6 pigment. Printex L6 was shown to be a more promising for H(2)O(2) production than Vulcan XC-72 R, while the latter was shown to have more potential for fuel cells. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of Different Light-Curing Modes on Degree of Conversion, Staining Susceptibility and Stain's Retention Using Different Beverages in a Nanofilled Composite Resin

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

An in vitro evaluation of apicoectomies and retropreparations using different methods

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of Conventional and Resin-modified Glass-Ionomer Liner on Dentin Adhesive Interface of Class I Cavity Walls After Thermocycling

Objective: The aim of this in vitro study was to analyze the effect of glass-ionomer cement as a liner on the dentin/resin adhesive interface of lateral walls of occlusal restorations after thermocycling.Materials and Methods: Occlusal cavities were prepared in 60 human molars, divided into six groups: no liner (1 and 4); glass-ionomer cement (GIC, Ketac Molar Easymix, 3M ESPE) (2 and 5); and resin-modified glass-ionomer cement (RMGIC, Vitrebond, 3M ESPE) (3 and 6). Resin composite (Filtek Z250, 3M ESPE) was placed after application of an adhesive system (Adper Single Bond 2, 3M ESPE) that was mixed with a fluorescent reagent (Rhodamine B) to allow confocal microscopy analysis. Specimens of groups 4, 5 and 6 were thermocycled (5 degrees C-55 degrees C) with a dwell time of 30 seconds for 5000 cycles. After this period, teeth were sectioned in approximately 0.8-mm slices. One slice of each tooth was randomly selected for confocal microscopy analysis. The other slices were sectioned into 0.8 nun x 0.8 mm beams, which were submitted to microtensile testing (MPa). Data were analyzed using two-way ANOVA and Tukey test (p < 0.05).Results: There was no detectedstatistical difference on bond strength among groups (alpha < 0.05). Confocal microscopy analysis showed a higher mean gap size in group 4(12.5 mu m) and a higher percentage of marginal gaps in the thermocycled groups. The RNIGIC liner groups showed the lowest percentage of marginal gaps.Conclusions: Lining with RMGIC resulted in less gap formation at the dentin/resin adhesive interface after artificial aging. RMGIC or GIC liners did not alter the microtensile bond strength of adhesive system/resin composite to dentin on the lateral walls of Class I restorations.

Evaluation of Ultrasonic and ErCr:YSGG Laser Retrograde Cavity Preparation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)